JPS6039165A - Activation of substance surface plating carrier material partially and directly - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for activating the surface of a carrier material which can be used for direct partial electroless plating, for example for producing printed circuit board assemblies.

This type of substrate assembly can be made in many different ways. Depending on the type of metal deposit, these various methods include semi-additive
process), fully add method
tive process), metal coating addition method (me
tal resist process) or substractive-additive method.
pr.

cess), and the so-called [multilayer film method (s+ulti
Layer technique) J is used [Guenther Hermann (Guenther Her+ma)
nn), “Printed circuit board manufacturing method and pretreatment method (
Leitplatten Herstellung u
ndVorbehandlung) J, Saulgau Wuertt, Germany
, Eugen 1 game 111/7x (Eugen G,
Lenze) Publishing Company, 1978, see here].

In the substrate underlining method, the carrier substrate is laminated to a copper foil by partially coating both sides with e.g. After removing the copper and rinsing the substrate, activating it with an activating solution, rinsing and sensitizing it, the entire plate is plated in a chemical plating bath.

The additive method, which directly creates a substrate assembly, consists of the following operational steps.

Coating with a carrier adhesion-promoting lacquer, etching the substrate with chromium sulfate, activating the lacquer film with an activating solution, coating the substrate surface with, for example, a screen-in-print φ lacquer or a photographic lacquer, and applying a new lacquer. The coating is partially developed, sensitized, chemically exposed to nickel or copper, and electrolytically thickened with electrically conductive metal deposits.

The activation solution used here is preferably an ionic or colloidal palladium solution or more recently a solution or dispersion of an organometallic compound (Austrian Patent No. 288,058, German Patent Publication No. (See Specification Ring No. 2,451,217 and No. 3,123.946).

From the brief description given above of known methods for partial plating of substrates, it can be seen that these methods are very labor-intensive. Furthermore, these methods are typically unable to create the desired fine electrically conductive pathways with geometries as complex as LLI11 and irreversibly degrade the matrix material.

Also, for oxidizing agents, such as chromate ions, which are trapped in the aqueous plating process, an activation bath, 1? Bathing and plating baths are irreversibly poisoned.

5- It is therefore an object of the present invention to avoid the above-mentioned disadvantages and, in particular, to eliminate the conventional post- or pre-treatments of the carrier, such as applying a mask, removing the mask chemically or physically or by etching. The object of the present invention is to provide a carrier having partial metal deposits that does not require a subsequent partial removal process of the metal deposits.

According to the invention, this purpose is achieved by selectively controlling the use of organometallic compounds of elements of subgroups 1 and 8 of the periodic table uniformly dispersed in an organic solvent as activators. spray-mist transfer method
tracing process), in particular by coating a portion of the substrate surface by the "ink fist mist method" or the "ink jet method".

[ink jet tra
cing process) J is generally known.

This is a printing ink method, in which droplets are controlled and sprayed onto the surface of the carrier without bringing the print head into contact with the surface of the carrier. Such methods are described, for example, in Siemens Journal, Volume 4, April 1977, pages 218-221.

According to this method υ:, information can be printed extremely quickly on a cellulose-based recording material 1-.

Piezoelectric effects are primarily used to control the printing nozzle and concomitantly trigger the ejection of droplets. A printing press operating on this principle is described, for example, in DE 2,543,457.

In contrast to the "ink jet method" in which the printing ink is accelerated and controlled by a signal voltage applied between a nozzle and an electrode placed opposite it, the similarly known "ink jet method"
In the ``ink mist method,'' an ink mist is created using ultrasonic vibrations.

Activators for organometallic compounds used in currentless plating of X-type surfaces are also generally known (Austrian Patent No. 288,058 and German Patent Application No.
In addition to No. 451,217, German Patent Publication No. 3,
No. 025,307, No. 3,148,280 and No. 3,
150°885).

These compounds include metal chelate complexes, organometallic π complexes (compounds) that have at least one other functional group in addition to the groups necessary to bind the metal, and oligomers, polymers, and preliminaries of organometallic compounds. It is a polymer.

Organometallic π complexes of Pd, Au, Pt, and Ag are preferred. Examples are butadiene-palladium dichloride, isoprene-palladium dichloride and benzoni I. liru dichloride palladium.

Particularly preferred are elements of the 1st and 8th subgroups of the periodic table with an oxidation degree of 1 to 4 (especially monovalent palladium), and a formula in which R and R4 are alkyl having 1 to 20 carbon atoms, preferably is alkyl having 1 to 6 carbon atoms, and R2 and R3 are hydrogen or alkyl having 1 to 4 carbon atoms, preferably methyl.

These complexes with unsaturated ketones are also partially known or can be produced by known methods.

Examples include mesityl oxide, n-budo-3-ene-2
-one, n-hept-3-en-2-one, n-hex-3-en-2-one, n-dec-4-en-3-one, 5-chlorobent-3-en-2 -one, ethyl vinyl ketone, 3-methyloct-5-en-4-one, 3
-methylbent-3-en-2-one, and 7-medoxyheptot-3-en-2-one.

Complexes derived from these compounds are characterized by high storage stability.

Suitable organic solvents for uniformly dispersing the activator include methylene chloride, chloroform, mesityl oxide, trichlorethylene, dichloroethane, acetone, methanol, ethanol, butanol, ethylene glycol, and the like. It is a mixture with a solvent.

9- Solvents or solvent mixtures which partially contaminate or partially swell the surface of the plastics to be plated are particularly suitable for carrying out the method of the invention in order to increase the adhesion of the metal deposit to the carrier surface. Preferably used.

In this regard, solvents and their combinations with precipitants are available from, for example, John Wiley and 5ons, New York, USA.
Published in 974, J-kai brand wrap (j, Br
undrup) and EΦH inner gut (E
, H. Innergut), "Polymer Handbook J.

However, without limiting the invention, when carrying out the method of the invention on a commercial scale, it is recommended that the following conditions be maintained.

1. The solvent is chemically and physically non-'t+' to the activator.
f It must not be adversely deteriorated.

ii. The solvent may cause coagulation or separation of the activator.
xing).

10-iii. The solvent must not completely dissolve or etch the carrier used.

iv. The solvent must be able to evaporate without extra post-treatment, such as UV irradiation or vacuum treatment.

Of course, organic polymers and latexes and/or organic or inorganic thickeners can be added to the activator-m liquid in order to impart the desired viscosity range or rheological properties. #Such elliptical additives which impart properties relating to intrinsic viscosity, chicktropy and giratancy or Newtonian filtration to the liquid solution are generally known [Ullmann (Ullmann et al.
llman), 2, 80; to,? +5.740;
and 17.107.192]. When selecting these sweat additives, the operating conditions of the equipment (printing speed, shear stress and shear force or shear rate in the nozzle) and the chemical and physical properties of the activating solution (e.g. viscosity, boiling point and swelling properties) )
must be taken into consideration.

vl, the activator solution must have a viscosity of 0.3 to 100 cp.

The novel method of the present invention is generally carried out as follows.

Elements of the 1st and 8th subgroups of the periodic table, especially Cu, Ag,
Organometallic compounds of Au, Pd, and pt are dissolved in an organic solvent. What is the concentration of organometallic compounds? 0.01 to 100 g per fL (regarding the metal used), preferably 0.1
~10.0g, particularly preferably 0.1~2.5g.

The activator solution is applied in the form of droplets, e.g.
After spraying onto a carrier using the "mist method", it is dried.

Examples of carriers suitable for the method of the invention include paper, polyethylene 1/
polypropylene, ABS plastics, epoxy resins, polyamide plastics, polyester plastics, polyacrylonitrile plastics, butadiene in styrene copolymer, amide/imide cocondensate,
Polyhydantoin, and these? # It is a mixture or copolymer of solids.

The partially activated carrier must then be reduced and sensitized. For this purpose, it is preferable to use the reducing agents customary in electrochemistry, such as hydrated hydrazine, phorol, aldehydes, hypophosphorous acid or poranes. ``The surface activated in this way can be used directly for currentless plating. However, it is necessary to remove the reducing agent residue from the surface by washing with water.

In a particularly preferred embodiment of the invention, sensitization in the plating bath is carried out using a reducing agent for currentless plating. This particularly preferred embodiment simplifies partial plating, which was not possible heretofore. This particularly simple embodiment consists of only three operations: direct activation of a part of the carrier, evaporation of the solvent and immersion of the activated surface in a plating bath.

This embodiment is particularly suitable for nickel-13 baths containing aminoporane, copper baths containing formalin, or chemical gold baths.

Suitable plating baths that can be used in the method of the present invention include Xi, Go,
A bath containing Cu, Au, or Ag salts or a mixture thereof. Such plating baths are known in currentless plating processes. If desired, such metal deposits can be increased to the desired thickness by chemical or electrolytic methods.

Products made according to the invention have many uses, such as printed circuits (printed electrical circuit board assemblies), metallic luster materials (decorative), and plastics made of electrostatically or electromagnetic shielding. carrier,
Identification cards, materials that magnetically carry or record and store information, pulsers and clock devices, materials that reveal hidden information by plating (partially activated after a desired period of time after printing), and materials with metallic luster. Used to manufacture carriers made of paper or plastics with characters, lines, etc. drawn on them. The invention is illustrated by the following examples. These Examples are for illustrative purposes only, and do not constitute the scope of the present invention other than the matters described in the claims.

Example 1 Size 2] AB of OX300mm, thickness O, Itam
S7 (lu, na, 0.75 g palladium(II) 4-cyclohexene-1,2-dicarphonate chloride, 8001
The film was partially activated using a conventional "ink jet method" using an activation solution made from 1.5 ml of ethanol and 50 ml of trichloroethane, the film was dried for 1 minute at room temperature, and then 3. Og dimethylaminoporan, 30
NiCl2 and 10 g of citric acid for 20 minutes in a chemical Ni bath with a concentrated ammonia solution to a pH of 8.2.
ss nickeling). A partially plated film was obtained. The coating thickness of the N1 deposit with metallic light waves was approximately 0.2 p-m.

Example 2 Size: 210 x 300 mm, thickness: 0, 05 mm (
7) Card made from Iy O-ce fiber,
0.5g butadiene dihaladium, 500ml
The card was partially activated by the conventional "Ink Miss I method" using an activation solution made from 1 cyclo8, 1 xanol, 200 ml ethylene glycol, and 50 ml mesityl oxide, and the card was kept at room temperature. for 5 minutes, sensitized for 3 minutes in an aqueous reducing bath containing 4.0 g of dimethylaminoporan in 11, followed by a conventional chemical copper bath [e.g. Solingen, Germany 58
50, Friedli Blasberg
Copper plating is carried out in a commercially available commercially available commercially available commercially available commercially available commercial product. After only 15 minutes, the test specimen was partially covered with the dressing.

About 25 minutes later.

The average thickness of this chemical copper deposit is approximately 0.2 m,
The width is approximately 75g, m. The test sample was removed from the chemical plating bath, washed with distilled water, and then electrolyzed in a copper electrolytic bath at a current density of 0.8/drn' for 30 minutes to increase the thickness of the deposit to approximately 6.6 μm. Ta.

Example 3 A 300 x 20 mm rectangular polyester film was activated according to Example 1 and, after evaporation of the solvent, 15
Nickel plated for minutes.

A partially plated film was obtained. The coating thickness of the N1 deposit with metallic luster was approximately 0.2 pLm.

Example 4 A 100 x 100 mm square polyamide film reinforced with glass fibers was cut into a 1.1.1-1-
A solution containing 0.6 g of acetonitrile palladium dichloride in dichloroethane was partially activated by the ink Φ mist method, and then currentless plating was performed as in Example 1. After only 30 seconds, the surface of the sheet was It started to partially turn black and after 3 minutes it was partially covered with fine Ni deposits. After about 15 minutes, the thickness of the chemically created Ni deposits was about Q,2 p,m. Similar results are obtained using palladium-r-complex of n-hept-3-enone.

Example 5 A 200 x 200 dragon square 17-square polyester film reinforced with glass fibers was coated with 0.9 g of isoprene-1.
2 g of cationic boron 1/tan.
latex, 200ml methanol, and 400ml
It consists of methylene chloride with a viscosity of 5. Activate according to Example 2 using a solution of Ocp, dry the film,
After sensitization, copper plating was performed for 25 minutes.

A partially plated plastinx component was obtained which was processed in a conventional electrolytic gold plating bath [e.g.
Friedlich Blasb
Full plating 17 with a thickness of about 40 gm was obtained.

Example 6 The hebutanone complex of Example 4 was prepared as follows.

6 g of an aqueous solution of Na2PdC:It containing 15% Pd was mixed with 20 g of freshly wood-fired n-hept-3-ene-
2-one over a period of 15 minutes at 110 DEG C., the mixture is stirred at this temperature for 25 minutes and then cooled to 0 DEG C.

-18 = After 2 hours, the bamboo-colored precipitate was suction filtered, washed three times with 75 ml of distilled water, and then washed with 50 ml of cold purified ethanol.
Washed twice, dried, toluene/trichloroethylene (1
: Recrystallize from 1) and vacuum dry in a dryer overnight. A pink-yellow crystalline solid with a decomposition point of 188° C. was obtained in a yield of 92%.

Patent applicant: Bayer Akchengezersha 19- 438-

Claims (1)

[Claims] 1. Using organometallic compounds of elements of the 1st and 8th subgroups of the periodic table evenly distributed in an organic solvent, the carrier material is partially directly electroless processed. A method of activating the substrate surface for plating, which selectively controls the transfer of these compounds using a spray mist transfer method, especially the "ink fist mist method".
Or a method characterized in that it is applied by the "ink fist jet method." 2. The method according to claim 1, wherein the treated substrate is removed from the solvent, sensitized as required, and then directly introduced into an electroless plating bath. 3. The method according to claim 1, wherein the activation is performed using an organometallic π compound of Au, Ag, Pd, Pt, and Cu or a +L mate complex. -1=4, the method according to claim 1, wherein the organometallic compound has at least one other functional group in addition to the group necessary for binding the metal. 5. Formula where R1 and R4 are alkyl having 1 to 20 carbon atoms, preferably alkyl having 1 to 8 carbon atoms, and R2 and R3 are hydrogen or alkyl having 1 to 4 carbon atoms, preferably methyl. The method according to claim 1, wherein the activation is performed using a complex compound of a saturated ketone. 6. The method according to claim 1, wherein the activation is carried out using palladium-IM form of boudo-3-en-2-one. 7. Organometallic compounds have a range of 0.1 to IO0.0 g/] (
2. The method according to claim 1, wherein the metal used is dissolved or dispersed in a solvent. 8. Cu, Ni, C (1, Al
1 or 2= The method according to claim 1, wherein a mixture thereof is used. 9. A method according to claim 1 for use in manufacturing a printed circuit board assembly.